WO2013133082A1 - Dispositif d'affichage à cristaux liquides et procédé de fabrication d'un dispositif d'affichage à cristaux liquides - Google Patents

Dispositif d'affichage à cristaux liquides et procédé de fabrication d'un dispositif d'affichage à cristaux liquides Download PDF

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WO2013133082A1
WO2013133082A1 PCT/JP2013/054896 JP2013054896W WO2013133082A1 WO 2013133082 A1 WO2013133082 A1 WO 2013133082A1 JP 2013054896 W JP2013054896 W JP 2013054896W WO 2013133082 A1 WO2013133082 A1 WO 2013133082A1
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liquid crystal
display device
crystal display
atom
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PCT/JP2013/054896
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Japanese (ja)
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昌行 兼弘
真伸 水崎
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シャープ株式会社
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Priority to US14/382,853 priority Critical patent/US10344216B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13712—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy

Definitions

  • the present invention relates to a liquid crystal display device and a method for manufacturing a liquid crystal display device. More specifically, the alignment layer of liquid crystal molecules is formed using a polymer layer (hereinafter also referred to as PSA (Polymer Sustained Alignment) layer) formed by polymerizing monomers contained in the liquid crystal composition without forming an existing alignment film.
  • PSA Polymer Sustained Alignment
  • the present invention relates to a liquid crystal display device for controlling properties and a method for manufacturing a liquid crystal display device suitable for forming a polymer layer.
  • Liquid crystal display devices are widely used as display devices such as televisions, personal computers, and PDAs because they are thin, light, and have low power consumption.
  • the size of liquid crystal display devices has been rapidly increasing, as represented by liquid crystal display devices for television.
  • a multi-domain vertical alignment mode (MVA) that can be manufactured with a high yield even in a large area and has a wide viewing angle is preferably used.
  • the liquid crystal molecules are aligned perpendicular to the substrate surface when no voltage is applied to the liquid crystal layer, so that a high contrast ratio is obtained compared to the conventional TN mode (TN: Twisted Nematic). be able to.
  • TN Twisted Nematic
  • the alignment film does not regulate the tilt direction of the liquid crystal molecules, but the tilt direction of the liquid crystal molecules is determined by the influence of protrusions (ribs) formed of an insulating material. Therefore, it is not necessary to perform an alignment treatment step on the alignment film, and static electricity and dust generated by rubbing or the like are not generated, so that a cleaning step after the alignment treatment is unnecessary. In addition, there is little variation in the initial tilt of the liquid crystal molecules, which is effective for simplification of the process, improvement of yield, and cost reduction.
  • a liquid crystal composition in which polymerizable components such as monomers and oligomers (hereinafter abbreviated as monomers) are mixed between substrates is sealed between substrates, and a voltage is applied between the substrates to tilt the liquid crystal molecules.
  • a pretilt angle imparting technique that forms a polymer layer by polymerizing monomers or the like in the state of being attracted attention see, for example, Patent Documents 1 and 2). Due to the influence of such a polymer layer, the liquid crystal has a predetermined pretilt angle even when the voltage application is removed, so that the tilt direction of the liquid crystal molecules is maintained even without the alignment film.
  • Such polymerization of monomers and the like is carried out by irradiation with heat or light (for example, ultraviolet rays).
  • X is an acrylate group or a methacrylate group.
  • R is an alkyl group having 1 to 18 carbon atoms or an alkoxy group.
  • c is an integer of 0-2.
  • d is 0 or 1.
  • the liquid crystal molecules are vertically aligned by the function of the polymer layer without forming the alignment film, but when c is 0, the light fleece dislocation occurs.
  • the light stability is low, causing a decrease in voltage holding ratio (VHR).
  • VHR voltage holding ratio
  • a polymerization initiator is necessary.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a liquid crystal display device in which display defects and a decrease in voltage holding ratio are unlikely to occur even when an alignment film is not formed. It is.
  • the inventors of the present invention have studied various types of monomers that can provide good display without forming an alignment film.
  • the lauryl acrylate represented by the formula is easily affected by alignment defects due to weak interaction with the liquid crystal molecules, and has been found to affect the display.
  • the present inventors conducted further diligent studies. As a result, at least two types of monomers mixed in the liquid crystal composition were used, and at least one of them produced a ketyl radical by a hydrogen abstraction reaction by light irradiation. It was found that the incorporation of a monomer having a structure can stabilize the orientation and maintain the voltage holding ratio.
  • the present inventors paid attention to the fact that the polymerization initiator remains in the liquid crystal layer because the conventional polymerization initiator does not have a polymerizable group.
  • the initiator By adding a polymerization initiator to the liquid crystal material and generating radicals efficiently in the liquid crystal layer by hydrogen abstraction reaction by light irradiation to promote polymerization, the initiator itself is taken into the polymer layer by polymerization, It has been found that the initiator component can be effectively phase separated from the liquid crystal layer.
  • a pair of substrates whose outermost surfaces are not substantially formed of an alignment film, a liquid crystal layer sandwiched between the pair of substrates and containing a liquid crystal material, and the pair of substrates And a polymer layer that controls the alignment of liquid crystal molecules, and the polymer layer is formed by polymerization of two or more kinds of radical polymerizable monomers added to the liquid crystal layer.
  • At least one of the radical polymerizable monomers formed is a liquid crystal display device which is a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation.
  • the configuration of the liquid crystal display device of the present invention is not particularly limited by other components as long as such components are essential.
  • the liquid crystal material may be either one having a positive dielectric anisotropy or one having a negative dielectric anisotropy, but adopts one having a negative dielectric anisotropy,
  • a vertical alignment (VA) mode liquid crystal display device with a high contrast ratio can be obtained.
  • one of the pair of substrates provided in the liquid crystal display device of the present invention is used as an array substrate and the other as a color filter substrate.
  • the array substrate includes a plurality of pixel electrodes, whereby the alignment of the liquid crystal is controlled on a pixel-by-pixel basis.
  • a plurality of color filters are arranged at positions where they overlap with the pixel electrodes of the array substrate, respectively, and the display color is controlled in units of pixels.
  • the outermost surfaces are not substantially composed of an alignment film.
  • the “alignment film” refers to a single layer film or a laminate composed of polyimide, polyamic acid, polyamide, polymaleimide, polysiloxane, polysilsesquioxane, polyphosphazene, or a copolymer thereof.
  • an alignment film material is directly applied (for example, application of polyimide or the like) or vapor deposition (for example, oblique deposition of silicon oxide (SiO)) on a substrate surface constituting a display region.
  • the display area is an area constituting an image recognized by the observer, and does not include, for example, a peripheral area such as a terminal portion.
  • the alignment film is not limited to those subjected to an alignment treatment as long as an existing alignment film material such as polyimide is applied. Examples of the material subjected to the alignment treatment include those subjected to rubbing treatment and photo-alignment treatment. Even without alignment treatment, for example, a vertical alignment film can align liquid crystal molecules perpendicular to the film surface, and a horizontal alignment film can align liquid crystal molecules horizontally with respect to the film surface. be able to. Further, when an alignment control structure is provided as in an MVA mode or a PVA mode described later, the tilt of liquid crystal molecules can be controlled without an alignment treatment.
  • a polymer layer for controlling alignment of liquid crystal molecules is formed on at least one surface of the pair of substrates, and two or more kinds of radical polymerizable monomers added to the liquid crystal layer are polymerized in the polymer layer. It is formed by.
  • the initial tilt of the liquid crystal molecules adjacent to the polymer layer can be tilted in a certain direction even if the alignment film is not provided.
  • the polymer layer is formed in a form having a structure in which the liquid crystal molecules are pretilt-aligned.
  • At least one of the radical polymerizable monomers is a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation.
  • the polymerization reaction can proceed in a short time without the need to add a new polymerization initiator, and impurities derived from the polymerization initiator are not generated, so that the voltage in the liquid crystal layer is maintained.
  • the rate (VHR) can be prevented from being lowered, and the deterioration of display quality can be reduced. Further, since light irradiation for a short time is sufficient, deterioration of components due to light irradiation for a long time can be prevented, and a highly reliable liquid crystal display device can be manufactured.
  • the ketyl radical is a radical generated when a carbonyl compound abstracts hydrogen from a hydrogen atom donor by photoexcitation.
  • Examples of the hydrogen atom donor include ethers, amines, thiols or alcohols having an alkyl group, an alkenyl group or an aralkyl group.
  • Examples of the compound having a structure that generates a ketyl radical include compounds having a benzophenone structure, a fluorenone structure, a thioxanthone structure, a benzyl structure, or an acetophenone structure in the molecule.
  • the structure for generating the ketyl radical is preferably a structure for generating a radical upon irradiation with a wavelength component of 330 nm or longer. Since there is an example in which the structure in the panel is deteriorated by irradiating a wavelength component of less than 330 nm and the performance as a display is impaired, the hydrogen abstraction type photopolymerization initiator bonded with a polymerizable group has a wavelength component of 330 nm or more. It is preferable to have a structure in which a hydrogen abstraction reaction is efficiently caused by irradiation to generate radicals.
  • the structure for generating the ketyl radical is more preferably a structure for generating a radical by irradiation with a wavelength component of less than 400 nm. Such a structure hardly absorbs light of 400 nm or more, which is light from a backlight (cold cathode fluorescent tube or LED) used for display in a general usage mode. The photopolymerization initiator phase-separated by polymerization without being pulled out does not react, and VHR can be kept high even in actual use.
  • the structure that generates the ketyl radical is more preferably a structure that generates a radical by irradiation with a wavelength component of 400 nm or more. As described above, since the light utilization efficiency is increased by having the absorption wavelength region up to the long wavelength side, the hydrogen abstraction type photopolymerization initiator bonded with the polymerizable group can efficiently cause the hydrogen abstraction reaction.
  • the benzophenone structure, fluorenone structure, thioxanthone structure, and benzyl structure have absorption with respect to light of 330 nm or more.
  • the fluorenone structure, thioxanthone structure, and benzyl structure also absorb light with a wavelength of 400 nm or more, and can be polymerized even by irradiation with light of a long wavelength component. Can be prevented.
  • the hydrogen abstraction reaction that generates a ketyl radical by light irradiation proceeds preferentially under the conditions in which a hydrogen atom donor exists, but in the absence of a hydrogen atom donor, photocleavage occurs. It is known that it has the property of generating radicals.
  • radical polymerizable monomer examples include those having a structure in which a polymerizable group is bonded to a hydrogen abstraction type photopolymerization initiator that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation.
  • a hydrogen abstraction type What has a structure represented by following Chemical formula (1) which is a photoinitiator is mentioned.
  • A1 and A2 are the same or different and each represents a structure containing a benzene ring, a biphenyl ring, or a linear or branched alkyl group or alkenyl group having 1 to 12 carbon atoms.
  • A1 and A2 Either of these includes a benzene ring or a biphenyl ring.
  • At least one of A1 and A2 includes a -Sp1-P1 group.
  • the hydrogen atom that A1 and A2 has is a —Sp1-P1 group, a halogen atom, a —CN group, a —NO2 group, a —NCO group, a —NCS group, a —OCN group, a —SCN group, a —SF5 group, or a carbon number
  • the alkyl group may be substituted with 1 to 12 alkyl groups or aralkyl groups, and the alkyl group may be linear or branched.
  • Two adjacent hydrogen atoms of A1 and A2 may be substituted with a linear or branched alkylene group or alkenylene group having 1 to 12 carbon atoms to form a cyclic structure.
  • the hydrogen atom of the alkyl group, alkenyl group, alkylene group, alkenylene group or aralkyl group of A1 and A2 may be substituted with a -Sp1-P1 group.
  • the —CH2-group of the alkyl group, alkenyl group, alkylene group, alkenylene group or aralkyl group of A1 and A2 is —O— group, —S— group, — unless the oxygen atom, sulfur atom and nitrogen atom are adjacent to each other.
  • P1 represents an acryloyloxy group, a methacryloyloxy group, a vinyl group, a vinyloxy group, an acryloylamino group, or a methacryloylamino group.
  • Sp1 represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a direct bond.
  • m is 1 or 2.
  • a dotted line portion connecting A1 and Y and a dotted line portion connecting A2 and Y indicate that a bond via Y may exist between A1 and A2.
  • Y represents a —CH 2 — group, —CH 2 CH 2 — group, —CH ⁇ CH— group, —O— group, —S— group, —NH— group, —N (CH 3) — group, —N (C 2 H 5) — group. , -N (C3H7)-group, -N (C4H9)-group, -OCH2- group, -CH2O- group, -SCH2- group, -CH2S- group, or a direct bond.
  • the compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation has any of the structures represented by the following chemical formulas (2-1) to (2-6). .
  • R1 and R2 are the same or different and are represented by a —Sp1-P1 group, a hydrogen atom, a halogen atom, —CN group, —NO2 group, —NCO group, —NCS group, —OCN group, —SCN group, —SF5 group, or an alkyl group, an aralkyl group, a phenyl group, or a biphenyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched. At least one of R1 and R2 includes a -Sp1-P1 group.
  • P1 represents an acryloyloxy group, a methacryloyloxy group, a vinyl group, a vinyloxy group, an acryloylamino group, or a methacryloylamino group.
  • Sp1 represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a linear bond.
  • the hydrogen atom that at least one of R1 and R2 has is a fluorine atom, a chlorine atom
  • the -Sp1-P1 group may be substituted.
  • the —CH2- group of R1 and R2 is —O— group, —S— group, —NH— group, —CO— group, —COO— group, —— unless the oxygen atom, sulfur atom and nitrogen atom are adjacent to each other.
  • the compound having any one of the structures represented by the chemical formulas (2-1) to (2-6) has an absorption wavelength range up to around 380 nm. Therefore, the polymerization can be started even if the cut filter is used to cut light having a short wavelength (for example, light having a wavelength of less than 330 nm) that affects the reliability of the liquid crystal.
  • More preferable compounds of the compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation include those having a structure represented by the following chemical formula (3-1) or (3-2). It is done.
  • R1 and R2 are the same or different and are represented by a —Sp1-P1 group, a hydrogen atom, a halogen atom, —CN group, —NO2 group, —NCO group, —NCS group, —OCN group, —SCN group, —SF5 group, or an alkyl group, an aralkyl group, a phenyl group, or a biphenyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched. At least one of R1 and R2 includes a -Sp1-P1 group.
  • P1 represents an acryloyloxy group, a methacryloyloxy group, a vinyl group, a vinyloxy group, an acryloylamino group, or a methacryloylamino group.
  • Sp1 represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a linear bond.
  • the hydrogen atom that at least one of R1 and R2 has is a fluorine atom, a chlorine atom
  • the -Sp1-P1 group may be substituted.
  • the —CH2- group of R1 and R2 is —O— group, —S— group, —NH— group, —CO— group, —COO— group, —— unless the oxygen atom, sulfur atom and nitrogen atom are adjacent to each other.
  • the compound represented by the chemical formula (3-1) or (3-2) has an absorption wavelength range up to around 430 nm. Therefore, since the light absorption wavelength range is wider and the light utilization efficiency is higher than that of the compound having any one of the structures represented by the chemical formulas (2-1) to (2-6), the light use efficiency is higher than 330 nm as described above. Even when light having a wavelength of is cut, the polymerization reaction rate by light irradiation in the production of a liquid crystal display device can be increased, and the throughput can be improved. Furthermore, since the absorption wavelength region extends to the long wavelength side, even after the polarizing plate is attached to each of the pair of substrates, light can be irradiated to polymerize the radical polymerizable monomer.
  • At least one other radical polymerizable monomer is preferably a radical polymerizable monomer having a ring structure and having a monofunctional or polyfunctional polymerizable group.
  • Preferred examples of the compound having the ring structure and having a monofunctional or polyfunctional polymerizable group include those having a structure represented by the following chemical formula (9).
  • R3 represents a —R4-Sp3-P3 group, a hydrogen atom, a halogen atom, a —CN group, a —NO2 group, a —NCO group, a —NCS group, a —OCN group, a —SCN group, a —SF5 group, or Represents a linear or branched alkyl group having 1 to 18 carbon atoms.
  • P3 represents an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinyl group, or a vinyloxy group.
  • Sp3 represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a direct bond.
  • the hydrogen atom which R3 has may be substituted with a fluorine atom or a chlorine atom.
  • -CH2- group possessed by R3 is an -O- group unless an oxygen atom and a sulfur atom are adjacent to each other; -S- group, -NH- group, -CO- group, -COO- group, -OCO- group, -O-COO- group, -OCH2- group, -CH2O- group, -SCH2- group, -CH2S- Group, -N (CH3)-group, -N (C2H5)-group, -N (C3H7)-group, -N (C4H9)-group, -CF2O- group, -OCF2- group, -CF2S- group,- SCF2- group, -N (CF3)-group, -CH2CH2- group, -CF2CH2- group, -CH2CF2- group, -CF2CF2- group, -CF2CF2- group, -CH2CF2- group, -CF2CF2- group, -CH2CF2- group, -CF2CF
  • A1 and A2 are the same or different and each represents 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene -2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, Decahydronaphthalene-2,6-diyl group, 1,2,3,4, -tetrahydronaphthalene-2,6-diyl group, indan-1,3-diyl group, indan-1,5-diyl group, indan- It represents a 2,5-diyl group, a phenanthrene-1,6-diyl group, a phenanthrene-1,8-diyl
  • the —CH2 group of A1 and A2 may be substituted with an —O— group or an —S— group unless they are adjacent to each other.
  • the hydrogen atom of A1 and A2 is substituted with a fluorine atom, a chlorine atom, a -CN group, or an alkyl group, alkoxy group, alkylcarbonyl group, alkoxycarbonyl group or alkylcarbonyloxy group having 1 to 6 carbon atoms. May be.
  • P2 represents an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinyl group, or a vinyloxy group.
  • A is 0 or 1.
  • b is 0 or 1.
  • s is 1 to 1.
  • 18 is a natural number of 18.
  • t is a natural number of 1 to 8.
  • x is a natural number of 1 to 3.
  • the compound having the structure represented by the chemical formula (4) has a high light stability and has a structure in which a light-Fleece transition does not occur upon irradiation with ultraviolet rays for forming a polymer layer, When used, a liquid crystal display device in which the voltage holding ratio is less likely to be reduced can be obtained.
  • the outermost surface of at least one of the pair of substrates is preferably composed of a silane coupling layer.
  • a silane coupling layer By disposing the silane coupling layer directly below the polymer layer, the hydrogen abstraction effect by the hydrogen abstraction type photopolymerization initiator can be further enhanced.
  • the presence of hydrogen in the functional group of the silane coupling compound contained in the silane coupling layer promotes the polymer polymerization reaction by the hydrogen abstraction type photopolymerization initiator and forms the polymer layer. It is possible to shorten the ultraviolet irradiation time required for.
  • silane coupling compound those having at least one functional group selected from the group consisting of a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, a mercapto group, and an isocyanate group are preferably used.
  • Another aspect of the present invention provides a liquid crystal composition containing a liquid crystal material and two or more types of radical polymerizable monomers between a pair of substrates whose outermost surfaces are not substantially composed of an alignment film.
  • at least one of the radical polymerizable monomers is a method for producing a liquid crystal display device which is a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation.
  • the method for producing a liquid crystal display device of the present invention comprises a liquid crystal composition containing a liquid crystal material and two or more radical polymerizable monomers between a pair of substrates whose outermost surfaces are not substantially composed of an alignment film. A step of clamping. Further, at least one of the radical polymerizable monomers is a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation.
  • the liquid crystal material and the radical polymerizable monomer the same materials as those described in the above-described liquid crystal display device of the present invention can be used.
  • the liquid crystal composition is irradiated with light, the radical polymerizable monomer is polymerized, and liquid crystal molecules are aligned on the surface of at least one of the pair of substrates. Forming a polymer layer.
  • the liquid crystal display device manufacturing method of the present invention adds a polymerization initiator newly by forming a polymer layer on the surface of the pair of substrates using the radical polymerizable monomer having the above-described characteristics.
  • the polymerization reaction can proceed in a short time without having to be performed, and since impurities derived from the polymerization initiator are not generated, the voltage holding ratio (VHR) in the liquid crystal layer is prevented from lowering and display quality deterioration is reduced. Can do. Further, since light irradiation for a short time is sufficient, deterioration of components due to light irradiation for a long time can be prevented, and a highly reliable liquid crystal display device can be manufactured. Furthermore, according to the manufacturing method of the present invention, the alignment of the liquid crystal molecules can be controlled and the decrease in the voltage holding ratio can be suppressed without forming an existing alignment film. This eliminates the need for additional manufacturing processes and capital investment.
  • the method for producing a liquid crystal display device of the present invention is not particularly limited by other steps as long as such steps are essential.
  • Preferred forms of the method for producing a liquid crystal display device of the present invention include the following forms (a) to (l) which are the same as those described as the preferred form of the liquid crystal display device of the present invention. That is, (A) The compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation is a compound represented by the above chemical formula (1), (B) the compound represented by the chemical formula (1) is a compound represented by any one of the chemical formulas (2-1) to (2-6), (C) the compound represented by the chemical formula (1) is a compound represented by the chemical formula (3-1) or (3-2), (D) a form in which at least one of the other radical polymerizable monomers is a radical polymerizable monomer having a ring structure and having a monofunctional or polyfunctional polymerizable group; (E) the form in which the radical polymerizable monomer having the ring structure and having a monofunctional polymerizable group is a compound represented by the chemical formula (9); (F) The
  • the silane coupling layer includes at least one functional group selected from the group consisting of a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, a mercapto group, and an isocyanate group.
  • the form in which the compound is contained (I) The liquid crystal material has a form having negative dielectric anisotropy, (J) The light used in the step of forming the polymer layer is a form having a wavelength component of 330 nm or more, (K) The light used in the step of forming the polymer layer is a light having a wavelength component of less than 400 nm, and (L) The light used in the step of forming the polymer layer may be in the form of light having a wavelength component of 400 nm or more.
  • the compound represented by the chemical formula (3-1) or (3-2) when used as a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation, an absorption wavelength region is around 430 nm. Therefore, even after the polarizing plate is attached to each of the pair of substrates, the polymer layer can be formed by irradiating the liquid crystal composition with light.
  • Examples of the step of forming the polymer layer include a mode performed in a state where a voltage equal to or higher than a threshold is applied to the liquid crystal layer.
  • a polymer is formed in a form following liquid crystal molecules that are aligned in a state where a voltage higher than a threshold is applied to the liquid crystal layer by applying light. Therefore, the formed polymer layer has a structure that defines the initial pretilt angle with respect to the liquid crystal molecules even if no voltage is applied later.
  • Examples of the step of forming the polymer layer include a mode that is performed in a state where a voltage higher than a threshold is not applied to the liquid crystal layer. Even in a state where a voltage higher than the threshold is not applied, it is possible to form a polymer layer for controlling the alignment of liquid crystal molecules, and the work necessary for voltage application can be omitted.
  • VHR voltage holding ratio
  • Embodiment 1 The liquid crystal display device of the present invention and the liquid crystal display device manufactured by the manufacturing method of the present invention can be used for display devices such as a television, a personal computer, a mobile phone, an information display, etc., and have excellent display characteristics. It can be demonstrated.
  • the liquid crystal display device according to the first embodiment includes a liquid crystal sandwiched between a pair of substrates including an array substrate 1, a color filter substrate 2, and the array substrate 1 and the color filter substrate 2.
  • Layer 5 The array substrate 1 includes an insulating transparent substrate made of glass or the like, various wirings formed on the transparent substrate, pixel electrodes, TFTs (Thin Film Transistors), and the like.
  • the color filter substrate 2 includes an insulating transparent substrate made of glass or the like, a color filter formed on the transparent substrate, a black matrix, a common electrode, and the like.
  • the liquid crystal layer 5 contains a liquid crystal material and two or more kinds of radical polymerizable monomers 4 and 6.
  • the liquid crystal material either a material having a positive dielectric anisotropy or a material having a negative dielectric anisotropy can be used.
  • one kind of radical polymerizable monomer 4 is a compound having a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation
  • the other kind of radical polymerizable monomer 6 is , A compound having a ring structure and having a monofunctional or polyfunctional polymerizable group.
  • the radical polymerizable monomer 4 By irradiating the liquid crystal layer 5 with light, the radical polymerizable monomer 4 generates a ketyl radical by a hydrogen abstraction reaction, and the radical polymerizable groups of the radical polymerizable monomers 4 and 6 are successively formed using the radical as an active species. Chain polymerization is started and advanced, and the polymer formed by the polymerization is deposited as a PSA layer 7 on the substrates 1 and 2 by phase separation as shown in FIG.
  • the radically polymerizable monomer 4 used in Embodiment 1 absorbs light alone and generates radicals to start chain polymerization, it is not necessary to administer a polymerization initiator. Moreover, since it has a polymerizable group, the polymerization initiator itself is taken into the PSA layer 7 by polymerization, so that the amount remaining in the liquid crystal layer 5 can be greatly reduced.
  • the liquid crystal layer 5 when performing the PSA polymerization step, the liquid crystal layer 5 is irradiated with light in a state where a voltage equal to or higher than the threshold is applied. Since the polymer is formed in such a shape, the formed PSA layer has a structure that defines the initial pretilt angle with respect to the liquid crystal molecules even if the voltage is not applied later. However, when two or more kinds of radically polymerizable monomers in the first embodiment are used even when the voltage exceeding the threshold is not applied to the liquid crystal layer 5 when performing the PSA polymerization step, It is possible to produce a PSA layer that induces orientation.
  • neither the array substrate 1 nor the color filter substrate 2 has an outermost surface composed of an alignment film, while the PSA layer 7 is formed on those surfaces. Is formed. Further, between the array substrate 1 and the color filter substrate 2, a sealing material 3 is directly attached on the substrates 1 and 2 along the outer edges of the substrates 1 and 2, and the liquid crystal layer 5 is sealed. The material 3 is sealed between the array substrate 1 and the color filter substrate 2. Further, since the light irradiation to the liquid crystal layer 5 is performed after the liquid crystal layer 5 is sealed with the sealing material 3, the PSA layer 7 is formed in a region surrounded by the sealing material 3.
  • the alignment of the liquid crystal molecules is defined by, for example, linear slits provided in pixel electrodes included in the array substrate 1 or common electrodes included in the color filter substrate 2 (PVA (Patterned Vertical (Alignment) mode).
  • PVA Plasma Exponed Vertical
  • the liquid crystal molecules have a uniform alignment toward the linear slit when a voltage is applied.
  • the PSA layer 7 that imparts a pretilt angle to the liquid crystal molecules can be formed.
  • Embodiment 2 The liquid crystal display device according to the second embodiment is the same as the liquid crystal display device according to the first embodiment, except that the outermost surface of the substrate is composed of a silane coupling layer.
  • silane coupling agent for forming the silane coupling layer examples include those having a structure represented by the following chemical formula (10).
  • R represents a methoxy group or an ethoxy group.
  • Y represents a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, a mercapto group, or an isocyanate group.
  • FIGS. 3 and 4 are schematic cross-sectional views of the liquid crystal display device according to the second embodiment.
  • FIG. 3 shows before the PSA polymerization step
  • FIG. 4 shows after the PSA polymerization step.
  • the outermost surfaces of the array substrate 11 and the color filter substrate 12 are constituted by the silane coupling layer 18.
  • One radical polymerizable monomer 14 generates a ketyl radical by irradiating the liquid crystal layer 15 with light, and the radical polymerizable property of the one radical polymerizable monomer 14 and the other radical polymerizable monomer 16 using the radical as an active species. Groups sequentially start and proceed with chain polymerization, and the polymer formed by the polymerization is deposited as a PSA layer 17 on the silane coupling layer 18 by phase separation as shown in FIG.
  • an alignment film 106 made of a polymer material (polyimide) having a main chain including an imide structure is formed on the surfaces of the array substrate 101 and the color filter substrate 102.
  • an alignment process such as a rubbing process or an optical alignment process on the surface of the alignment film 106, the pretilt angle of the liquid crystal molecules can be oriented vertically or horizontally (initially tilted).
  • a sealing material 103 is attached between the array substrate 101 and the color filter substrate 102 along the outer edges of the substrates 101 and 102, and the liquid crystal layer 105 is connected to the array substrate 101 and the color filter by the sealing material 103.
  • the alignment film 106 needs to be formed by applying a polyimide solution or the like before sealing with the sealing material 103, the alignment film 106 is also formed under the sealing material 103.
  • a material for forming the alignment film 106 in addition to the polyimide, a material containing at least one of polyamic acid, polyamide, polymaleimide, polysiloxane, polysilsesquioxane, polyphosphazene, or a copolymer thereof. Is mentioned.
  • a compound represented by the above chemical formula (1) can be used, and more specifically, The compounds represented by the above chemical formulas (2-1) to (2-6) or the above chemical formula (3-1) or (3-2) can be used.
  • the compound represented by the chemical formula (1) has a structure that generates a ketyl radical by a hydrogen abstraction reaction by light irradiation, there is no need to add another polymerization initiator when mixing with a liquid crystal material.
  • the polymerization reaction can be efficiently started only by light irradiation.
  • impurities that are likely to be charged which are presumed to originate from the polymerization initiator, are taken into the PSA layer by the bonded polymerizable group, for example, the chemical formulas (6-1) to (6-7) It is possible to make image sticking less likely to occur than when a PSA layer is formed using a polymerization initiator that does not have a polymerizable group.
  • Embodiments 1 and 2 other monomers can be added to the liquid crystal composition.
  • the compound represented by the chemical formula (9) can be used, and more specifically, the compound represented by the chemical formula (4) can be used. Since the compound represented by the chemical formula (4) has sufficient interaction with the liquid crystal molecules, stable alignment can be obtained only with the PSA layer without forming an alignment film. Since it has a structure that does not cause light fleece transition upon irradiation with ultraviolet rays for forming a PSA layer, for example, a monomer having low light stability as represented by the above chemical formula (8) is used alone. It is possible to make it difficult for the voltage holding ratio to be lowered as compared with the case where the layer is formed.
  • the array substrate 1, the liquid crystal layer 5, and the color filter substrate 2 are stacked in this order from the back side of the liquid crystal display device to the observation surface side.
  • a polarizing plate is provided on the back side of the array substrate 1.
  • a polarizing plate is also provided on the observation surface side of the color filter substrate 2.
  • a retardation plate may be further arranged for these polarizing plates, and the polarizing plate may be a circularly polarizing plate.
  • the liquid crystal display device may be any of a transmission type, a reflection type, and a reflection / transmission type. If it is a transmission type or a reflection / transmission type, the liquid crystal display devices of Embodiments 1 and 2 further include a backlight. The backlight is arranged further on the back side of the array substrate 1 and arranged so that light passes through the array substrate 1, the liquid crystal layer 5, and the color filter substrate 2 in this order.
  • the array substrate 1 includes a reflection plate for reflecting outside light. Further, at least in a region where reflected light is used as a display, the polarizing plate of the color filter substrate 2 needs to be a circularly polarizing plate provided with a so-called ⁇ / 4 retardation plate.
  • the liquid crystal display device according to the first embodiment and the second embodiment may be in the form of a color filter on array having a color filter on the array substrate 1. Also, The liquid crystal display device according to the first and second embodiments may be a monochrome display. In that case, the color filter does not need to be arranged.
  • the liquid crystal layer 5 is filled with a liquid crystal material having a characteristic of being oriented in a specific direction when a constant voltage is applied.
  • the orientation of the liquid crystal molecules in the liquid crystal layer 5 is controlled by applying a voltage higher than a threshold value.
  • the alignment mode of the liquid crystal molecules includes, for example, TN mode, IPS mode, VA mode, and the like.
  • a monofunctional acrylate monomer represented by the following chemical formula (12) is used. In such a case, since excellent vertical alignment regulating force can be obtained, it is more preferable to apply to a mode in which the initial alignment such as VA mode and TBA mode is vertical alignment.
  • the liquid crystal display device is obtained by disassembling a liquid crystal display device (for example, a mobile phone, a monitor, a liquid crystal TV (television), an information display) and performing nuclear magnetic resonance analysis (NMR: Nuclear Magnetic Resonance). ), Fourier transform infrared spectroscopy (FT-IR: Fourier Transform Infrared Spectroscopy), mass spectrometry (MS: Mass Spectrometry), etc., to perform analysis of monomer components present in the PSA layer, The abundance ratio of monomer components present in the PSA layer, the residual amount of monomers contained in the liquid crystal layer, and the like can be confirmed.
  • a liquid crystal display device for example, a mobile phone, a monitor, a liquid crystal TV (television), an information display
  • NMR Nuclear Magnetic Resonance
  • FT-IR Fourier transform infrared spectroscopy
  • MS mass spectrometry
  • Example 1 in which a liquid crystal cell included in the liquid crystal display device according to Embodiment 1 was actually produced is shown below.
  • a liquid crystal composition containing a liquid crystal material having negative dielectric anisotropy and a radical polymerizable monomer was injected between the pair of substrates.
  • the sealing material any one that is cured by heat, one that is cured by irradiation with ultraviolet light, or one that is cured by either heat or ultraviolet light irradiation may be used.
  • monomers represented by the following chemical formula (11) and the following chemical formula (12) were used in combination.
  • the compound represented by the following chemical formula (11) is a benzophenone-based bifunctional methacrylate monomer
  • the compound represented by the following chemical formula (12) is a biphenyl-based monofunctional acrylate monomer.
  • the monomer After injecting the liquid crystal composition, the monomer is polymerized by irradiating the substrate with non-polarized ultraviolet light (0.33 mW / cm 2) from the normal direction for 15 minutes (0.3 J / cm 2) with no voltage applied. went.
  • non-polarized ultraviolet light source a black light FHF-32BLB manufactured by Toshiba Lighting & Technology was used.
  • FHF-32BLB is an ultraviolet light source having a small emission intensity at 310 nm and a large emission intensity at 330 nm or more.
  • the electrode a flat electrode without a slit was used.
  • radicals are generated by extracting hydrogen present in the system by carbonyl groups excited by light irradiation. Then, the polymerizable group of the monomer is successively bonded to this radical, and a polymer is formed so as to grow in a chain manner.
  • the compound represented by the chemical formula (11) has an absorption wavelength range up to about 380 nm, and therefore has a short wavelength light that affects the reliability of the liquid crystal (for example, less than 330 nm The polymerization can be started even if the light having a wavelength of 1 is cut.
  • Example 1 the introduction amount of the benzophenone-based bifunctional methacrylate monomer represented by the chemical formula (11) was 0 wt%, 0.01 wt%, 0.05 wt%, 0 wt% with respect to the entire liquid crystal composition, respectively. Four types of samples with 15 wt% were prepared. Moreover, about the biphenyl type monofunctional acrylate monomer represented by the above chemical formula (12), the introduction amount was fixed at 1.0 wt% with respect to the entire liquid crystal composition. Below, the result of having verified the characteristic about each is shown.
  • VHR voltage holding ratio
  • FIGS. 7 to 10 are photographic diagrams showing the state of each liquid crystal cell under crossed Nicols after ultraviolet irradiation.
  • FIGS. 7 to 10 respectively show the introduction amounts of the polymerization initiator monomer represented by the chemical formula (11) with respect to the entire liquid crystal composition of 0 wt%, 0.01 wt%, 0.05 wt%, and 0.15 wt%. The state of the liquid crystal cell is shown.
  • the introduction amount of the polymerization initiator monomer represented by the chemical formula (11) is 0 wt% with respect to the entire liquid crystal composition, the liquid crystal molecules are not vertically aligned, but when 0.01 wt%, the liquid crystal molecules are vertically aligned. A vertical alignment cell having no alignment defect was obtained at 0.05 wt% or more. Further, the VHR tends to decrease as the introduction amount increases, but the VHR has a high value of 97% or more even at 0.15 wt%.
  • the pixel portion of the liquid crystal cell is not displayed in black, and the liquid crystal molecules are not vertically aligned at all, whereas in FIG. Became black display, and liquid crystal molecules were not partially aligned vertically.
  • FIGS. 9 and 10 the pixel portion of the liquid crystal cell is almost completely black, and the liquid crystal molecules are vertically aligned over the entire surface.
  • Example 2 in which a liquid crystal cell included in the liquid crystal display device according to Embodiment 2 was actually produced is shown below.
  • a pair of substrates having a transparent electrode on the surface is prepared, and the surface of the pair of substrates is represented by the following chemical formula (14) without passing through the step of forming an alignment film;
  • a silane coupling layer was formed, a sealing material was applied to one substrate, beads were dispersed on the other substrate, and then bonded. Subsequently, a liquid crystal composition containing a liquid crystal material having negative dielectric anisotropy and a radical polymerizable monomer was injected between the pair of substrates.
  • a sealing material any one that is cured by heat, one that is cured by irradiation with ultraviolet light, or one that is cured by either heat or ultraviolet light irradiation may be used.
  • silane coupling agent using the compound represented by the chemical formula (14) dissolved in water or an organic solvent onto the substrate, as shown in FIG. 11, silane coupling is performed on the outermost surface of the substrate. After the agent is hydrolyzed, dehydration condensation is performed to form a silane coupling compound.
  • a carbonyl group in a hydrogen abstraction type photopolymerization initiator excited by light irradiation generates a radical by extracting hydrogen present between a pair of substrates into which the liquid crystal composition is injected, thereby generating radical polymerization.
  • the ultraviolet light irradiation time can be shortened.
  • the monomer was polymerized by irradiating the substrate with non-polarized ultraviolet light (0.33 mW / cm 2) from the normal direction in the state where no voltage was applied.
  • the non-polarized ultraviolet light source and the electrodes were the same as those in Example 1.
  • Example 2 Two types of samples were prepared: a liquid crystal cell using a substrate whose surface was treated with the silane coupling agent, and a liquid crystal cell using a substrate not treated with a silane coupling agent.
  • the introduction amount of the benzophenone-based bifunctional methacrylate monomer represented by the chemical formula (11) is 0.15 wt% with respect to the entire liquid crystal composition, and is represented by the chemical formula (12).
  • the amount of the biphenyl-based monofunctional acrylate monomer introduced was fixed at 1.0 wt% with respect to the entire liquid crystal composition. Below, the result of having verified the characteristic about each is shown.
  • VHR voltage holding ratio
  • Example 3 in which a liquid crystal cell included in the liquid crystal display device according to Embodiment 1 is actually manufactured will be described below.
  • a sealing material to one substrate without passing through the step of forming an alignment film, spread beads on the other substrate, and bond them together went.
  • the sealing material any one that is cured by heat, one that is cured by irradiation with ultraviolet light, or one that is cured by either heat or ultraviolet light irradiation may be used.
  • the monomer was polymerized under the same conditions as in Example 1.
  • the compound represented by the chemical formula (15) has an absorption wavelength region up to about 440 nm as shown in the absorption spectrum of FIG. 12, so even if light with a short wavelength that affects the reliability of the liquid crystal is cut off. Polymerization can be initiated.
  • Example 3 the introduction amount of the benzylic bifunctional methacrylate monomer represented by the chemical formula (15) was 0 wt%, 0.01 wt%, 0.05 wt%, 0 wt% with respect to the entire liquid crystal composition, respectively. Four types of samples with 15 wt% were prepared. Moreover, about the biphenyl type monofunctional acrylate monomer represented by the above chemical formula (12), the introduction amount was fixed at 1.0 wt% with respect to the entire liquid crystal composition. Below, the result of having verified the characteristic about each is shown.
  • VHR voltage holding ratio
  • the introduction amount of the polymerization initiator monomer represented by the chemical formula (15) is 0 wt% with respect to the entire liquid crystal composition, the liquid crystal molecules are not vertically aligned, but when 0.01 wt%, the liquid crystal molecules are vertically aligned. A vertical alignment cell having no alignment defect was obtained at 0.05 wt% or more. Further, the VHR tends to decrease as the introduction amount increases, but the VHR has a high value of 97% or more even at 0.15 wt%.
  • Example 4 in which a liquid crystal cell included in the liquid crystal display device according to Embodiment 2 was actually produced will be described below.
  • a pair of substrates having a transparent electrode on the surface is prepared, and the pair of substrate surfaces are treated with the silane coupling agent represented by the above chemical formula (14) without passing through the step of forming an alignment film.
  • a silane coupling layer was formed, a sealing material was applied to one substrate, beads were dispersed on the other substrate, and then bonded.
  • a liquid crystal composition containing a liquid crystal material having negative dielectric anisotropy and a radical polymerizable monomer was injected between the pair of substrates.
  • the sealing material any one that is cured by heat, one that is cured by irradiation with ultraviolet light, or one that is cured by either heat or ultraviolet light irradiation may be used.
  • the monomers represented by the chemical formula (15) and the chemical formula (12) were used in combination.
  • Example 4 In Example 4, two types of samples were prepared: a liquid crystal cell using a substrate whose surface was treated with the silane coupling agent, and a liquid crystal cell using a substrate not treated with a silane coupling agent.
  • the introduction amount of the benzylic bifunctional methacrylate monomer represented by the chemical formula (15) is 0.15 wt% with respect to the entire liquid crystal composition, and represented by the chemical formula (12).
  • the amount of the biphenyl-based monofunctional acrylate monomer introduced was fixed at 1.0 wt% with respect to the entire liquid crystal composition. Below, the result of having verified the characteristic about each is shown.
  • VHR voltage holding ratio
  • the ultraviolet light irradiation time required for forming the PSA layer can be shortened, and a high voltage holding ratio of 98% or more can be obtained. could be maintained.

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Abstract

L'invention se rapporte à un dispositif d'affichage à cristaux liquides qui risque moins d'afficher des défauts et de présenter une diminution du rapport de maintien de tension même lorsqu'un film d'orientation n'est pas formé. Ce dispositif d'affichage à cristaux liquides comprend : une paire de substrats dont la surface la plus éloignée n'est pratiquement pas dotée d'un film d'orientation ; une couche de cristaux liquides placée entre la paire de substrats et contenant un matériau à cristaux liquides ; ainsi qu'une couche de polymère située sur la surface d'au moins un substrat de la paire de substrats afin de commander l'orientation des molécules de cristaux liquides. La couche de polymère est obtenue grâce à la polymérisation d'au minimum deux types de monomères polymérisables de façon radicalaire ajoutés dans ladite couche de cristaux liquides. Au moins un monomère polymérisable de façon radicalaire est un composé qui possède une structure générant un radical cétyle à l'aide d'une réaction d'abstraction d'hydrogène par le biais d'une photoirradiation.
PCT/JP2013/054896 2012-03-05 2013-02-26 Dispositif d'affichage à cristaux liquides et procédé de fabrication d'un dispositif d'affichage à cristaux liquides WO2013133082A1 (fr)

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